CN102149652B - Ceramic material, method for the manufacture of a ceramic material and electroceramic component comprising the ceramic material - Google Patents
Ceramic material, method for the manufacture of a ceramic material and electroceramic component comprising the ceramic material Download PDFInfo
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Abstract
Ceramic material of the general formula: [SE1-xMIIx][Cr1-y-zRyLz]O3, wherein SE stands for one or more rare earth metals, MII stands for one or more metals of the oxidation state +II, L stands for Al and/or Ga, R stands for one or more metals selected from Fe, Zn, Ge, Sn, and it holds that: 0<x<1; 0<y<1; 0.5<z<1; y+z<1.
Description
The problem of widely touching upon that is used as the stupalith of thermistor (Hei β leiter) is, the resistance of this stupalith has the B-constant, though this constant satisfies the requirement to thermistor sensitivity, the B-constant value under high temperature range has caused too little resistance value to the actual measurement technology for detection.
Thermistor means a kind of electro-conductive material, this material under comparatively high temps than more conducting electricity at a lower temperature.The resistance of this material raises with temperature and descends.Be that this class material has negative temperature coefficient, so be also referred to as NTC-material (negative temperature coefficient).Can measure rational curve to NTC-material or the electroceramics member that contains this material.It can be described by following Arrhenius equation (Arrheniusbeziehung):
R
T=R
NExp [B* (1/T-1/T
N)] or ρ
T=ρ
NExp [B* (1/T-1/T
N)]
R wherein
TBe resistance, ρ
TBe the resistivity under the temperature T.R
NBe the good nominal temperature T of agreement
NUnder resistance, as T
N=25 ℃.This B-constant is corresponding to merchant E
A/ k, wherein E
ABe the thermal activation energy, k is Boltzmann constant (Boltzmannkonstant).R
TWith ρ
TPress formula R through geometrical factor
T=ρ
T* L
k/ A
kBe associated, wherein A
kBe the contact surface of the parallel sample of face, L
kIt is the spacing between the contact surface.This thermal activation can be represented the activation energy at polaron conduction (Polaronenleitung), and usually based on certain temperature range, for example based on for B
25/100 ℃Interval based on 25-100 ℃.
The charged particle carrier that polaron means electronics is the related of phonon with lattice vibration, and it is associated in and is called quasi-particle in theory.
In addition, this B-constant is and the measuring of the sensitivity α of temperature correlation that the resistance of the electroceramics member relevant with temperature is represented in this sensitivity:
α=?1/ρ
T?(dρ
T?/dT)?=?-?B/T
2
The purpose of embodiment of the present invention is to provide a kind of stupalith at room temperature (~ 25 ℃) thermometric to 1000 ℃ the temperature range, and this material has high permanent stability.
This purpose is to realize by the stupalith of claim 1.This stupalith and other embodiments that contain the electroceramics member of this stupalith are themes of other claim.In addition, also claimed for the preparation of method of ceramic material.
A kind of embodiment of the present invention relates to the stupalith of following general formula:
[SE
1-xM
II x][Cr
1-y-zR
yL
z]O
3
Wherein, SE is one or more rare earth metals, M
IIBeing one or more oxidation valencys is the metal of+II, and L is Al and/or Ga, and R is one or more metals that are selected from Fe, Zn, Ge, Sn, and 0<x<1; 0<y<1; 0.5<z<1; Y+z<1.
This stupalith can pass through general formula ABO
3Describe, wherein SE and M
IIPlace A-position and Cr, L and R place beta-position.The resistance of this stupalith is by the incompatible adjusting of suitable groups of these components.This resistance can be by introducing L at the beta-position of pottery and also introducing R and realize with " dilution " Cr.R and the selected element of L are preferably had charge migration equivalence (Ladungstransportindifferenz), and namely its oxidation valency in the lattice of this stupalith is determined.On the contrary, Cr can change its oxidation valency.This charge migration is subject to polaron-place-exchange-process of Cr in whole temperature range.
In another embodiment, R represents just in time two kinds of metal R
1And R
2, this general formula is thus:
[SE
1-x-pM
II x+p][Cr
1-y-z-rR
2 p+rR
1 yL
z-p]O
3
Wherein, if R
2=R
2 IV, also be the positively charged ion of the redox-stable of oxidation valency IV, then p and r satisfy: 0.001<p<0.05 and r=0, and if R
2=R
2 II, also be the positively charged ion of the redox-stable of oxidation valency II, then 0.001<r<0.05 and p=0.To the situation of p=0, by introduce the positively charged ion R of the redox-stable of oxidation valency II at the beta-position of uhligite-structure
2As Zn
IICan realize Cr
IVThe increase of-concentration.This can do not introduce one or more other have concentration and its activation energy of realizing fine setting current carrier center (polaron) under the transition-metal cation situation of conversion valency.Can increase electroconductibility thus, but because the increase than great fluctuation process and the B-constant that is associated thus in the lattice current potential (Gitterpotential), this electroconductibility increase can be compensated into partly even overcompensation, this causes the resistance increase, and corresponding to following formula:
[SE
1-xM
II x][Cr
III 1-x-y-z-2rCr
IV x+rZn
II rR
1 yL
z]O
3
Or the formula of pressing:
[SE
1-x-pM
II x+p][Cr
III 1-x-y-zCr
IV xR
2IV pR
1 yL
z-p]O
3
R=0, R
2=R
2 IV=Ge and/or Sn are with Cr
III/ Cr
IVKeep constant than the polaron concentration that is associated.Thus only by since the part of tetravalence Ge and/or Sn introduce to replace the current carrier center (polaron) that Tricationic R and L such as L=Al cause potential energy distribution big irregularity and thus the irregularity of B-constant just cause that resistance increases.
Wherein, SE is one or more rare earth metals, M
IIBeing one or more oxidation valencys is the metal of+II, and L is Al and/or Ga, and R is that one or more are selected from the metal of Cr, Al, Ga and Mn and to p=0, R
2=Zn
IIWith to r=0, R
2=R
2IV=Ge and/or Sn, and p=0 o'clock satisfy 0<x<1; 0≤y<1; 0.5<z<1; 0.05<1-y-z<1 and 0.001<r<0.05, and when r=0,0.001<p<0.05.
This stupalith can pass through general formula ABO
3Describe, wherein SE and M
IIPlace A-position and Cr, L, Zn or Ge and/or Sn and R (as long as existence) place beta-position.The resistance of this stupalith is by the incompatible adjusting of suitable groups of these components.This resistance can be by introducing L and randomly also introduce R and R at the beta-position of pottery
2=Zn
IIOr Ce
IVAnd/or Sn
IVRealize with " dilution " Cr.To R and L and R
2Selected element preferably has the charge migration equivalence, and namely its oxidation valency in the lattice of this stupalith is determined.On the contrary, Cr can change its oxidation valency.This charge migration is subject to polaron-place-exchange-process of Cr in whole temperature range.By dilution effect, Zn
IIAnd R
2 IV=Ge, Sn be owing to the fluctuation of having widened the lattice current potential helps to increase the B-constant, at this moment can avoid introducing have mixed valence at high temperature to disadvantageous other transition-metal cation of charge migration.
In another embodiment of the invention, SE is one or more elements that are selected from Y, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Lu.Wherein Y is preferred.
The feature of these rare earth metals all is, its at the oxidation valency for being stable under the+III situation.For the present invention, to mean ordination number be 39 and the element of 57-71 to rare earth metal.
In another embodiment of the invention, SE is a kind of rare earth metal just in time.
In another embodiment of the invention, M
IIBe one or more elements that are selected from Mg, Ca and Sr.Wherein Ca and Sr are preferred.Element M g, Ca and Sr exist with oxidation valency+II.To containing Ca and/or Sr as M
IIStupalith, with L=Al and/or Ga is combined and adding under Zn or Ge and/or the Sn situation, can reach extraordinary resistance value and B-constant, comprise high ageing resistance.
In another embodiment of the invention, M
IIIt is a kind of element just in time.
Selecting Ca or Sr as M
IIStupalith in, with L=Al and/or Ga is combined and adding under Zn or Ge and/or the Sn situation, can reach extraordinary resistance value and B-constant and high ageing resistance.
In another embodiment of the invention, R is Fe or the metallic combination that comprises Fe.To containing Fe as the stupalith of R, with L=Al and/or Ga is combined and can reach extraordinary resistance value and B-constant and high ageing resistance under the situation of randomly adding Zn or Ge and/or Sn.
In another embodiment of the invention, R is Zn or the metallic combination that comprises Zn.
In another embodiment of the invention, R is Ge or the metallic combination that comprises Ge.
In another embodiment of the invention, R is Sn or the metallic combination that comprises Sn.
The inventor is known, if a kind of element such as Cr with mixed valence only
III/ Cr
IVParticipate in conductive mechanism and do not use other redox couple such as Mn
III/ Mn
IV, then can prepare and have being suitable at the thermometric stupalith of room temperature (~ 25 ℃) to 1000 ℃ of temperature ranges of high permanent stability.Obtaining uniformly thus in whole temperature range almost is constant B-value, and at this moment this resistance can be only by positively charged ion such as the Al of Cr by redox-stable
IIIOr Ga
IIIInstitute part replaces regulates, and by being that the positively charged ion Zn of redox-stable or Ge and/or Sn can be aligned to resistance specific value equally in the extra introducing of the beta-position of perovskite crystalline lattice, but coefficient z must satisfy: 0.5<z, and to satisfy the resistance needs.Avoid introducing multiple different transition-metal cation with mixed valence in this way, guarantee that simultaneously enough variations in the lattice current potential are to be transferred to enough big B-constant.
This stupalith can be by the general formula ABO of perovskite structure type
3Describe, wherein SE
IIIAnd M
IIPlace A-position and Cr, L and the R that chooses wantonly and Zn or Ge and/or Sn place beta-position.By introduce two valency positively charged ion M in the A-position
IIInduce Cr by guiding valence state (gelenkt Valenz) principle at beta-position
IVFormation, itself and Cr
IIIForm redox couple together, to cause high polaron conductivity.Because adjacent Cr only
III/ Cr
IV-to participating in conduction, so this resistivity can be by introducing the positively charged ion L (Al of the redox-stable of " dilution " polaron concentration at the beta-position of perovskite crystalline lattice
IIIOr Ga
III) regulate, wherein finely tune by introducing additional realization of Zn or Ge and/or Sn.This element al
IIIAnd/or Ga
IIIAnd interpolation Zn
IIOr Ge
IVAnd/or Sn
IVThe also rare earth metal SE that introduces in the A-position
IIIAnd metal M
IIDetermined+III or+II or+the oxidation valency of IV, and therefore be helpless to polaron place-exchange process.
By with Y
IIIBe used for SE
IIIWith with Ca
IIBe used for M
II, with L=Al and/or Ga is combined and be issued to extraordinary resistance value and B-constant adding Zn or Ge and/or Sn situation.
In another embodiment, R is the just in time a kind of metal that is selected from Fe, Zn, Ge, Sn.
In another embodiment of the invention, SE
IIIBeing the oxidation valency is just in time a kind of rare earth metal of+III.To selecting Fe
IIIAs R
III, do not find that this resistance-temperature-rational curve that uses 400-500 ℃ of scope turns to steeper trend, namely has bigger B-constant.Can reason out this Fe thus
IIIBe redox-stable at desired conditions.So Cr exists as the unique component that is two kinds of different oxidation valencys.This polaron-place-exchange-process is subject to Cr thus.By guiding valence state principle, in stupalith, pass through M
IIContent regulate Cr
IVContent, and finely tune by adding Zn.Should be as Cr in mixture of starting material
IIIThe Cr that exists when the preparation pottery by the oxidation of atmospheric oxygen institute.
In another embodiment of the invention, parameter x satisfies: 0.03≤x≤0.5, wherein preferred 0.05<x<0.25.
In another embodiment of the invention, parameter y satisfies: 0<y<0.5, wherein preferred 0.005<y<0.25.
In another embodiment of the invention, parameter z satisfies: 0.5<z<0.9, wherein preferred 0.70<z<0.90.
In another embodiment of the invention, parameter y and z satisfy: 0.05<(1-y-z)<0.25, and wherein preferable range 0.10<(1-y-z)<0.20.
In another embodiment of the invention, parameter p or r satisfy: in p=0 o'clock 0.001<r<0.05 with in r=0 o'clock 0.001<p<0.05.
Stupalith with these parameters can reach extraordinary resistance value and B-constant.
In another embodiment of the invention, this stupalith is ABO as general formula
3The uhligite-mixed crystal system of homogeneous phase form.
The crystalline structure of this uhligite can be with two kinds of dissimilar descriptions.
This B-atom respectively is octahedral structure by 6 Sauerstoffatoms and centers on.Should [BO
6]-octahedra becomes three-dimensional network through total dihedral.The A-atom is present in the network room, and this A-atom has by 12 Sauerstoffatoms and is coordination sphere that cuboctahedron forms as coordination polyhedron.
Alternatively, this structure also can be used as cube the closeest spherical accumulation and describes, and this spherical accumulation is made of jointly A-atom and oxygen.Per four octahedral voids of this spherical accumulation are occupied by the B-atom.
This stupalith can be thermistor-resistive material, namely at high temperature than the material that is easier at low temperatures conduct electricity.The resistance of this material raises with temperature and descends.
Polaron-place-exchange-process is by so-called " jump " realization between the different oxidation valencys of the stable transition-metal cation of non-oxide reduction.Except Cr
III/ Cr
IVOutward, also exist the stable oxidation valency of other non-oxide reduction for+III and+the element E of IV so that not only can realize Cr
III/ Cr
IVAnd E
III/ E
IVBetween jump, also can realize E
III/ Cr
IVAnd Cr
III/ E
IVBetween jump.By hop limit is arrived a kind of element, be Cr in the case, then can increase average jump spacing, this causes current path to descend and resistance increases.The contriver knows, the existence of the element E that other the non-oxide reduction that can help polaron-jump is stable can cause, for example will take steep trend for Mn as the resistance-temperature-rational curve of situation in 400 ℃ of-500 ℃ of scopes of E, and have bigger B-constant thus.Its result is, can have low resistance value at 1000 ℃ to thermometric, is not more than ≈ 10 if the resistance of room temperature is transferred to
6Ω cm, then a few Ω cm only for example.Can stop resistance-temperature-characteristic steep trend in this temperature range by removing the stable metal of other non-oxide reduction except Cr to stop additional hop path, this causes, and is not more than ≈ 10 if the resistance of room temperature is transferred to
6Ω cm, 1000 ℃ still reach at least tens Ω cm the resistance of striving realizing.
In certain embodiments of the invention, necessary inventive step is to recognize, the existence of a plurality of different redox couples is as except such as Mn
IIIAnd Mn
IVOuter Cr in addition
IIIAnd Cr
IVHave and help from Cr
IIITo Mn
IVOr from Mn
IIITo Cr
IVThe additional activation of polaron-place-exchange process, it uses and causes that resistance-temperature-rational curve turns to steep trend, namely has bigger B-constant 400-500 ℃ of scope.Consequently, be not more than about 10 if the resistance of room temperature is transferred to
6Ω cm has then caused the only low excessively resistance value of a few Ω cm to the thermometric at 1000 ℃ thus.
Therefore, only redox couple such as Cr of restriction
IIIAnd Cr
IVBe associated, be not more than ≈ 10 if consequently the resistance of room temperature is transferred to as avoiding resistance-temperature-curve to lead to steep trend in the basis of the polaron-course of conveying in the uhligite mixed crystal system of forming by described formula and the high temperature range
6Ω cm, also can 1000 ℃ reach at least tens Ω cm the resistance of striving realizing.
Safeguarding the permanent stability that require corresponding to defined and during until 1000 ℃ ageing resistance, the essence of embodiment of the present invention is to cause at uhligite-mixed crystal system ABO by getting rid of second redox couple
3In the milder trend of resistance-temperature-rational curve, the effect that wherein be used for to change one of second redox couple of the potential energy on the polaron lattice position is by adding Zn
IIOr Ge
IVAnd/or Sn
IVObtain, and also keep the enough sensitivity of this thermometric thus.
Except this stupalith itself, this method of ceramic material of claimed preparation also.
A kind of embodiment for the preparation of the method for ceramic material of one of above-mentioned embodiment comprises following method steps: A) mix following compounds: SE
2O
3, M
IICO
3, Cr
2O
3, L
2O
3With the oxide compound of R, to form mixture, B) sintering A) in made mixture.
In the first method steps A) in, mixing raw material SE
2O
3, M
IICO
3, Cr
2O
3, L
2O
3Oxide compound with R.Wherein Cr is as Cr
2O
3Add, namely with wherein as Cr
IIIThe compound that exists adds.At the second method steps B) namely with also have M
IICO
3The sintering of other raw material in, Cr
III(pass through M
IIThe content guiding) is oxidized to Cr through atmospheric oxygen with the equivalent share
IVIn the uhligite-mixed crystal system of sintering, realizing charge neutralization (positive cationic charge and negative oxide ion electric charge equivalence) thus.
In the other method flexible program, this raw material is settled out from aqueous phase, and drying and then sintering.
In the other method flexible program, at method steps B) before, this raw mix is also through calcining.Calcining temperature is 1000 ℃-1300 ℃, wherein preferred 1050 ℃-1200 ℃ scope.
In the other method flexible program, at method steps B) before, this material through calcining is also through grinding.By grinding the granularity d of the particle that can get
50Be about 1 micron.Granularity d
50Provide the size of the granularity that about 50% particle has.
In the other method flexible program, follow aforesaid grinding also through the correct grinding step.Granularity d behind correct grinding
50Be the 0.3-1 micrometer range.
In the other method flexible program, by method steps B) sintering form the uhligite-mixed crystal system of homogeneous phase.It is available general formula ABO
3The isotropic phase of describing.
In the other method flexible program, at method steps B) in sintering carry out at 1400 ℃-1600 ℃, wherein preferred 1550 ℃-1600 ℃ is at least 90% of theoretical density to reach enough sintered densities.
Except this stupalith, the claimed electroceramics member that contains this stupalith also.
A kind of embodiment of this member comprises the stupalith of one of previous embodiments.
In the another embodiment of this member, this member comprises the matrix of the stupalith that contains one of previous embodiments and a plurality of conduction contacts on this matrix surface.These a plurality of conduction contacts for example can comprise platinum.
Wherein, a kind of embodiment of this member can so design, and makes this member be applicable to thermometric.
Because this stupalith can be the NTC-material, it for example is applicable to temperature sensor.This member for example can be designed to thermistor thus.This thermistor for example can be used for to the thermometric of 1000 ℃ of temperature ranges.This member is so moulding for example, to be suitable as the Abgassensor of oil engine, particulate filter or catalyst converter.
The rational curve that comprises the thermistor of stupalith of the present invention does not have or only has very little timeliness drift (zeitlich Drift), at comparatively high temps enough ageing resistance is arranged also thus.And have the favourable resistance of measuring technology namely in room temperature resistance<10
6Ω cm is tens Ω cm at 1000 ℃ of resistance, simultaneously this B-constant and thus this sensitivity all do not have too strongly and to reduce.
Study 8 kinds of different stupalith A to H below, wherein this stupalith A to F relates to the embodiment of stupalith of the present invention, and stupalith G and H are non-Comparative Examples of the present invention:
A?[Y
0.95Ca
0.05][Cr
III 0.09Cr
IV 0.055?Zn
II 0.005Al
III 0.85]O
3
B?[Y
0.95Ca
0.05][Cr
III 0.08Cr
IV 0.06?Zn
II 0.01Al
III 0.85]O
3
C?[Y
0.945Ca
0.055][Cr
III 0.10Cr
IV 0.05?Ge
IV 0.005Al
III 0.845]O
3
D?[Y
0.94Ca
0.06][Cr
III 0.10Cr
IV 0.05?Ge
IV 0.01Al
III 0.84]O
3
E?[Y
0.945Ca
0.055][Cr
III 0.10Cr
IV 0.05?Sn
IV 0.005Al
III 0.845]O
3
F?[Y
0.94Ca
0.06][Cr
III 0.10Cr
IV 0.05?Sn
IV 0.01Al
III 0.84]O
3
G:?[Y
0.97Ca
0.03][Cr
III 0.12Cr
IV 0.03Fe
III 0.85]O
3
H:[Y
0.97Ca
0.03] [Cr
III 0.12Cr
IV 0.03Mn
III 0.085Al
III 0.765] O
3Or
[Y
0.97Ca
0.03][Cr
III 0.15Mn
IV 0.03?Mn
III 0.055?Al
III 0.765]O
3。
Here this non-composition H of the present invention can pass through two kinds of limit structrual descriptions, because Cr and Mn can reduce or oxidation mutually.The oxidation valency of this element is from+III to the+transformation of IV and the transformation combined generation of another element of this two element from+IV to+III thus.
Composition A to F of the present invention is the stupalith with negative temperature coefficient, and it also satisfies the requirement to the favourable resistance value of measuring technology simultaneously under the high thermostability and ageing resistance situation up to 1000 ℃, namely be about 10 in the room temperature maximum
6Ω cm is at least tens Ω cm at 1000 ℃, simultaneously this B-constant and thus this sensitivity all do not have too strongly and to reduce.
Be the powder of preparation stupalith, each uses following composition (% provides with weight):
A:?64.22%?Y
2O
3、3.00%?CaCO
3、6.60%?Cr
2O
3、0.24%?ZnO、25.94%?Al
2O
3
B:?64.21%?Y
2O
3、3.00%?CaCO
3、6.37%?Cr
2O
3、0.49%?ZnO、25.94%?Al
2O
3
C:?63.81%?Y
2O
3、3.29%?CaCO
3、6.82%?Cr
2O
3、0.31%?GeO
2、25.76%?Al
2O
3
D:?63.40%?Y
2O
3、3.59%?CaCO
3、6.81%?Cr
2O
3、0.63%?GeO
2、25.58%?Al
2O
3
E:?63.72%?Y
2O
3、3.29%?CaCO
3、6.81%?Cr
2O
3、0.45%?SnO
2、25.73%?Al
2O
3
F:?63.22%?Y
2O
3、3.58%?CaCO
3、6.79%?Cr
2O
3、0.90%?SnO
2、25.51%?Al
2O
3
G:?57.10%?Y
2O
3、1.57%?CaCO
3、5.94%?Cr
2O
3、35.39%?Fe
2O
3
H:?64.56%?Y
2O
3、1.77%?CaCO
3、6.72%?Cr
2O
3、22.99%?Al
2O
3、3.96%?Mn
2O
3。
This each raw material is all weighed with 200-300 g deionized water and pre-the grinding.At 1050 ℃-1150 ℃ powder is carried out the calcining first time after drying, carried out 4 hours.Then use the main grinding of carrying out waterborne suspension through the zirconium ball of stabillzed with yttrium, reach d with this
50Target size less than 1.5 μ m.Through again dry and 1100 ℃-1200 ℃ powder carried out calcining 4 hours second time after the enforcement smooth grinding to granularity d
50Less than 0.8 μ m.
For the preparation sample, this ceramic powder is mixed with tackiness agent, make to be transformed into slurry, and be processed into mobile compressed granulate then to make the sheet stampings or it is sent to the film pulling process to make diaphragm behind lamination by injection.
Electrical connection on the NTC-pottery is to realize with silk screen printing as electric interface by applying the Pt-paste on two major surfacess of sheet sample or diaphragm.Not only electric interface is burnt in the ceramic matrix by means of co-sintering afterwards, and also this stupalith of sintering.By unsticking mixture technology commonly used, this sintering at the most 1600 ℃ carry out, the residence time is 1-3 hour.
The NTC-member that so makes is evaluated its stability by the measurement of resistance in stable temperature range, and confirms the aging drift of electricity during corresponding high temperature storage and by the rational curve of periodically drawing up to 1000 ℃.For measuring electrical parameter, it is that 5.5 mm and Gao Ge are the columniform ceramic sample with conduction platinum contact surface of 1.5 mm that diameter is provided.
Work embodiment A of the present invention is to the electrical property value ρ of F
25 ℃, B
25/100 ℃And B
300/1000 ℃List in table 1.
Table 1:
For ceramic sample B and D, each is to detect resistance and B-constant and C.T. curve three measuring periods, with the evaluation ageing resistance.The observed value of B gained is listed in table 2a-c, the observed value of D gained is listed in table 3a-c.These heating and cooling are stepped to be carried out, and the waiting time is at least 30 minutes.
Table 2a: sample B
Table 2b: sample B
Table 2c: sample B
Table 3a: sample D
Table 3b: sample D
Table 3c: sample D
From these tables, can find out B
300/1000And ρ
300The maximum of (Δ B and Δ ρ) changes in the period 1 appearance, reduces but should change subsequently, and this shows inevitable preconditioning.The result confirms, can eliminate the drift that beginning is found out by preconditioning suitable, that randomly periodically implement.
Below by annexed drawings set forth work embodiment of the present invention.
Fig. 1 illustrates the Arrhenius figure of ceramic A to F of the present invention and the Arrhenius figure of non-compound G of the present invention and H sample.
Fig. 2 illustrates the schematic side elevation of the embodiment of this electroceramics member.
Fig. 1 work embodiment A of the present invention shown in the Arrhenius figure to F and non-embodiments of the invention at 300 ℃-1000 ℃ electricalresistivity's (Ω cm) rational curve, under the G situation, equally only contain redox couple Cr
III/ Cr
IV, this non-sample H of the present invention also contains redox couple Mn
III/ Mn
IVFigure intermediate value 1000/T draws with electricalresistivity's logarithm, and wherein T represents the absolute temperature represented with Kelvin.In order to demarcate, to provide another scale at upside, and draw auxiliary line by this scale in the drawings.This scale be with temperature (℃) expression temperature scale.
Work embodiment A of the present invention to resistance-temperature-rational curve of F has shown required mild trend and has also guaranteed enough sensitivity simultaneously and also safeguard given requirement and permanent stability and ageing resistance simultaneously.This is to be found out by table 2a-c and 3a-c.
This rational curve shows, non-sample H of the present invention is because its characteristic big steepness (higher B-constant) is not suitable as the NTC-material is used in 25 ℃ of-1000 ℃ of temperature ranges: the resistance of room temperature surpass that practical application considers 10
6The several magnitude of Ω cm.
As can be seen from Figure 1, non-ceramic H of the present invention has bigger rational curve steepness (bigger B-value is arranged thus) 800-1000 ℃ of scope internal ratio in 300-500 ℃ of scope, and this application to the thermistor till room temperature can cause resistance too high; The resistivity of this ceramic sample H in the time of 25 ℃ greater than 10
8Ω cm.Though this non-ceramic sample G of the present invention is linear trend, this linearity trend is owing to only there being F
III, but by replacing Al with Fe, this resistance further reduces, so that can not satisfy the resistivity requirement of tens Ω cm.Comparison shows that as the value of two compd Bs in his-and-hers watches 1 and table 2 and the table 3 and D the feature of pottery of the present invention in 25-1000 ℃ whole temperature range is the B-constant of basically identical separately.This B-constant in the periodicity heating and cooling through just confirming in admissible tolerance zone after the period 1 that it is constant.
Fig. 2 illustrates the schematic side elevation of a kind of embodiment of this electroceramics member 1.This member comprises ceramic matrix 2, its downside dispose first conductive contact surfaces 10 and thereon side dispose second conductive contact surfaces 15.
Reference numerals list:
1 member
2 ceramic matrixs
10 first conductive contact surfaces
15 second conductive contact surfaces
The rational curve of A-F pottery of the present invention
G, the rational curve of the non-pottery of the present invention of H.
Claims (15)
1. the stupalith of following general formula:
[SE
1-xM
II x][Cr
1-y-zR
yL
z]O
3
Wherein, SE is one or more rare earth metals, M
IIBeing one or more oxidation valencys is the metal of+II, and L is Al and/or Ga, and R is one or more metals that are selected from Fe, Zn, Ge and Sn, and satisfies: 0<x<1; 0<y<1; 0.5<z<1; Y+z<1; 0.1<1-y-z<0.2.
2. the stupalith of claim 1, wherein, SE is one or more elements that are selected from Y, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Lu.
3. the stupalith that one of requires of aforesaid right, wherein, M
IIBe one or more elements that are selected from Mg, Ca, Sr and Ba.
4. the stupalith of claim 1, wherein, R is Fe or the metallic combination that comprises Fe.
5. the stupalith of claim 1, wherein, R is Zn or the metallic combination that comprises Zn.
6. the stupalith of claim 1, wherein, R is Ge or the metallic combination that comprises Ge.
7. the stupalith of claim 1, wherein, R is Sn or the metallic combination that comprises Sn.
8. the stupalith that one of requires of aforesaid right, wherein, parameter x satisfies: 0.03≤x≤0.5.
9. the stupalith that one of requires of aforesaid right, wherein, parameter y satisfies: 0<y<0.5.
10. the stupalith that one of requires of aforesaid right, wherein, parameter z satisfies: 0.5<z<0.9.
11. the stupalith of one of aforesaid right requirement is as general formula ABO
3The uhligite-mixed crystal system of homogeneous phase form.
12. the stupalith of one of aforesaid right requirement, wherein, this stupalith has negative temperature coefficient.
13. for the preparation of the method for ceramic material of one of aforesaid right requirement, it comprises following method steps:
A) mix following compounds: SE
2O
3, M
IICO
3, Cr
2O
3, L
2O
3With the oxide compound that also has optional R, with the formation mixture,
B) sintering is at A) in made mixture.
14. the electroceramics member comprises the stupalith of one of claim 1-12.
15. the electroceramics member of claim 14 comprises:
-ceramic matrix (2),
-be configured in lip-deep two conductive contact surfaces of this ceramic matrix (2) (10,15).
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DE102008046858A DE102008046858A1 (en) | 2008-09-12 | 2008-09-12 | Ceramic material, method for producing a ceramic material, electroceramic component comprising the ceramic material |
PCT/EP2009/061818 WO2010029156A1 (en) | 2008-09-12 | 2009-09-11 | Ceramic material, method for the manufacture of a ceramic material and electroceramic component comprising the ceramic material |
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KR101220312B1 (en) * | 2012-06-28 | 2013-01-10 | 태성전장주식회사 | Ceramic composition for thermistor temperature sensor and thermistor element peepared by the composition |
CN107564641A (en) * | 2017-08-21 | 2018-01-09 | 西北工业大学 | A kind of NTC thermistor semiconductive ceramic composition |
DE102020126833A1 (en) | 2020-10-13 | 2022-04-14 | Tdk Electronics Ag | Sensor arrangement and method for manufacturing a sensor arrangement |
CN115594503B (en) * | 2022-12-14 | 2023-04-14 | 中国人民解放军国防科技大学 | Calcium and iron co-doped NdAlO 3 Ceramic material and preparation method and application thereof |
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CN1138204A (en) * | 1995-03-27 | 1996-12-18 | 株式会社日立制作所 | Ceramic resistor, production method thereof neutral grounding resistor and circuit breaker |
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